Method of refining petroleum oils



Feb. 26, 1929. 1,703,615

O. DIECKMANN METHOD OF REFINING PETROLEUM OILS Filed Sept. 1' 1921 2 Sheets-Sheet l and [03] aasolz n6 Removed Feb 26, 1929 1,703,615

0. DIECKMANN 7 METHOD OF REFI-NING PETROLEUM OILS Filed Sept. 1. 1921 2 Sheets-Sheet 2 I y. '5- 69 I 69 1 l gwuentoz Patented Feb. 26, 1929 UNITED STATES PATENT OFFICE.

OTTO DIEOKIANN, 01' CINCINNATI, OHIO.

IETHOD O1 DEFINING PETBOLEFI OILS.

a nmm fledleptember 1, 1921. swam). 491,645.

My invention relates to improvement in method of refining petroleum oils. One of its objects is to avoid breaking down or destroying hydrocarbons, as for instance 011s and resinous com ounds contained originally in the crude oil, y subjecting them to temperatures at which they decompose. Anotherobject is to separate or remove certain asphalt paraffin and oil compounds and mineral salts and substances before subjecting the crude oil to heat for fractional separation of the illuminating or fuel and lubricating oils by distillation. Another object is to produce illuminating and fuel oils and lubricating oils free from products resulting from the destructive distillation of other substances and compounds. Another ob ect is to recover lubrlcatin oils of higher flash point than customar' y produced heretofore. Another object is to increase the percentage yield of lubricating oils. Another object is to separate the asphalt and paraflin substances 1n .the form of cokeless hard pitch as one. of the end products. Another object is to simplify the method of refining, and'to reduce the amount of loss or waste incident to refining. My invention also comprises certain novel steps and order of procedure, all of WhlCh will be fully set forth in the description of the accompanying drawings in which 1:

Fig. 1 represents diagrammatically an apparatus and order of procedure adapted to the practice of my improved method.

Fig. 2, is a central vertical section through one of the containers illustrated in Fig. 1.

Fig. 3, is a View similar to Fig. 2, illustrating one of the containers of Fig. 1 with the agitating apparatus removed. I v

n the accompanying drawings a series of tanks or fluid containers are provided and preferably arranged so that the liquids may flow by gravity from one container to another, as may be required. Where the transfer from one container to another can not be conveniently attained by gravity, pumps, pneumatic, mechanical, or other conveyors may be employed to transfer the substances from one container to another.

In Figs. 2 and 3 I have illustrated the general character of container repeatedly em-.

nels. As illustrated in Figs. 2, and 3, the several containers and each comprise havinga conical bottom 61, a removable lid 62 or if desired a permanent lid with a manhole therein. A vertical shaft 63 is provided with agitator blades 64, and also preferably a conduit 65 to supply compressed air to agitate the contents of the container. A stock supply conduit 66, a steam pi e 67 nearthe upper end of the container an a steam pipe 68 near the bottom of the container are provided, said steam pipes being each connected up and adapted to serve .as a live steam sup- 8 y pipe or as a steam escape pipe, the steam eing employed to warm or heat and also to agitate the-contents of the container and also to assist in flushing and cleaning the containers. At the bottom the containers are supplied preferabl with three way valves 69 adapted tobe adjusted to conduct a lower layer of liquid from the container, or to suecessively conduct two or more layers of liquid from the container along the conduits 69" and 69" to different destinations. A valve controlled ofitake conduit 7 0 is also referably provided near the lower end of t 1e container to enable one or more upper layers of liquid to be withdrawn leaving the lower layer in the container undisturbed. As illus trated the agitator shaft 63, blades 64 and lid 62 and journal spider 71 are adapted to be lifted from one container and applied to agitate the contents of another container, but may be permanently located if desired.

. The crude oil as it comes from the wells varies somewhat in composition, and contains-certain asphaltum, paraffin and mineral salts and substances and resinous compounds and oils which are not classified under the regular group or chain of hydrocarbon oils, and some of which when subjected to the higher degrees of heat heretofore usually employed in the fractional distillation of petroleum oils are destroyed or broken down into other compounds or substances, some of which are driven over with and serve to dilute the true hydrocarbon oils or to contaminate them while other portions escape as gases or remain in the residue as a needless waste product. One of the objects attained by my improved method is to separate certam of these compounds and substances from the medium or illuminating and lubricating oils before the medium and lubricating oils are fractionally distilled or subjected to a sufiiare preferably lead lined a cylindrical portion pounds and substances.

' compounds,

In the drawings 15 represents one or more containers in which the crude oil to be treated is .stored. From the storage reservoir 15 crude petroleum oil is periodically conducted to a container 16 by means of a valve controlled conduit 17. In the container 16 the crude oil is treated to remove the small percentage of water usually carried by crude oils. Theremoval of the watermay be eifected by the addition of substances having a strong af-v finity for water, or by other means. The

crude oil free from water is then periodical1y conducted by means of a valve controlled conduit 18 to a container 19, which serves as a still, to which .a mild degree of heat is applied, sufficient to drive off the more volatile substances such as benzine and gasoline which are condensed and conducted by means of a valve controlled conduit 20 to a storage reservoir 21 from which they may be marketed or further fra'ctionally separated and then marketed.

The crude oil free from the water and more volatile products is then conducted by'means of a valve controlled conduit 22 to acontainer 24, preferably .substantially as shown in Figs. 2 and 3. In the container 24 the crude oil is mixed with a quantity of sulphuric acid in concentrated condition from the storage reservoir 23, slowly added, and the oil and acid thoroughly mixed and agitated for about twenty minutes, whereby an emulsion ofacid, dissolved resins, and other organic and mineral salts, asphaltum, and paraffin compounds is formed as a lower layer in container 24 while an upper layer contains chiefly the hydrocarbon oils largely freed from asphaltum, parafiimmineral compounds, and other substances carried into the acid sludge or emulsion. The acid emulsion or sludge is conveyed from container 24 to container 30 by means of a valve controlled conduit 29, and the acidulated oils or supernatant fluid from container 24 is conducted by valve controlled conduit 32 to a container 33.

The acid sludge emulsion in container 30 is agitated and subjected to live steam until it reaches a temperature of approximately degrees C. The agitation is then stopped and the steam cut off entirely or cut down to a small amount about sufiicient to maintain the temperature uniform, whereupon the emulsion separates into two layers, a lower one acid sludge containing mineral; salts, asphaltum, paraifin, resinous, and other organic compounds, and an upper layer consisting chiefly of acidulated oil. While still warm the acidulated oil from container 30 is run into a settling reservoir 25, where the small residue of acid sludge separates out at the bottom, and the acidulated oil goes on preferabl to the container 33 where it mixes with t eacidulated oil from the container 24. The acid sludge slowly accumulatin in the lower portion of container 25 is withdrawn from time to time and returned to container 30.

The acid sludge remaining in container 30 is not allowed to 'cool and has added thereto from a storage reservoir 26 through valve controlled conduit 27 a quantity of-warm refinedpetroleum oil, illuminating oil forinstance, and the refined petroleum and acid sludge agitated 'for approximately twenty minutes. The agitator is stopped and the mixture allowed to stand quiescent for about an hour with only sufficient steam to maintain: a substantially uniform temperature, whereupon a lower layer of acid sludge is formed containing the mineral salts, the bulk of the asphaltum and paraflin compounds, and other organic substances, and a supernatant layer containing the extracting medium (refined petroleum) together with such extractable oils, resins, and substances as have been extracted from the acid sludge into the refined petroleum. -This last step would be to a certain extent a reversal of a previous step, in that it seeks to recover into the acidulated oil substances previously separated therefrom into the acid sludge. The refined petroleum and extracted matter from container 30 .are preferabl conveyed to the container 33 and mixed w1th the acidulated oils therein for further treatment. The extracting operation in container 30 is repeated, for instance three or four times, and then I the acid sludge from container 30 is conveyed to a container 36 for further treatment If desired the oils and substances recovered and extracted from the acid sludge in container 30 instead of-being mixed with the contents of container 33 may be treated and refined separately from the contents of container 33, and in a parallel line of containers and substantially as hereinafter described for the refinement of the acidulated oils in container 33. I

The acid sludge in container 36 which has been repeatedly extracted with refined petroleum in container 30 has added thereto an amount of tar oil or crude benzene which is employed as an extracting medium to extract the remaining substances of value from the acid sludge, after the tar oils and acid sludge have been agitated together at a temperature of approximately 90 degrees C. and with an addition of water to about one third of the volume for about ten minutes, the agitation is stopped and the contents of container allower to stand quiescent for about an hour to separate into two layers. The'lower layer of extracted acid sludge is run to waste through a valve controlledconduit 36 or used for fertilizers and the supernatant liquid comprising the'tar oils and extracted matslightly and while live steam is admitted to raise its ter is conducted forward through conduit 36" to a container 37, where it is warmed being agitated is neutralized with sodium hydroxide of specific gravit of about 1.10 for instance, to show an alhaline reaction, and the agitation continued for five minutes. Sufficientheat is supplied to maintain the temperature and the contentsof container 37 allowed to stand quiescent for about one to two hours to separate into. two layers. The lower layer free from oils is run to waste, while the upper layer is refined to yield a hard pitch free from coke stored in container 37 and a cylinder oil of high flash point, stored in container 37 while the tar oils are recovered for future use as an extracting medium.

The acidulated oils' and extracts conveyed from time to time to container 33 from containers 24, 25 and 30 are subjected to agitation and have added thereto in a slow stream a quantity of concentrated sulphuric acid from the reservoir 23 through a valve controlled conduit 23'. Agitation is continued from 15 to 20 minutes, sufiicient steam is admitted to maintain the temperature, and the contents of container allowed to stand quiescent for about an hour until it has separated into two layers, acid sludge which is run ofi and added to the acid sludge of container 30, and acidulated oil. The above operation of washing the acidulated oils in container 33 is repeated two or three times, adding the acid sludge each time to the acid sludge in container 30, after which the washed acidulated oil is allowed to stand quiescent for about two hours and then run off from container 33 into a settlin reservoir or container 39. The oil entering the settling reservoir 39 is green in color and substantially free from asphaltum, and is allowed to stand uiescent in container 39 to allow resinous su stances and possibly other substances held in suspension to settle out.

The acidulated oil is conducted forward from container 39 to a container 40 where temperature to approximately 80 to 90 degrees C. and the contents of container 4Q'agitated. A 4% solution of carbonate of soda, about 10 to 15% by weight of the oil is added in container 40 from reservoir 41 and agitation continued for about fifteen minutes. The contents of container 40 is then allowed to stand quiescent for about an hour to separate into different layers. A layer of soda lye of alkaline reaction and brown color is then drawn off to a storage reservoir 41' and may be used with a new addition of soda: as a neutralizing material.

The neutralized oils remaining in container 40 are then agitated and washed with from '20 to 25% by weight of warm water for about five minutes after which the contents of container 40 separates into three .acid sludge with refined petroleum oil to layers, a lower watery solution which is run 0 to waste, a second yellowish brown emulsion, which is run ofi to a storage recervoir 42, and a layer of neutralized greenish colored oil which is run off to a storage reservoir 43.

The emulsion in the container 42 is heated by means of a live steam coil 42 which causes it to further separate into an up or layer of greenish oil which is added to t e greenish oil in container 43, and a raw soap or soap stock which is conveyed to a reservoir 44 for sale or use in soap makin or in the gen1- eration of illuminating and uel gas.

The greenish oils accumulated in the storage reservoir 43 are conveyed forward to a container or still 45 where they are fractionally distilled. As illustrated they are separated roughly into two'fractions one of which is conveyed to a storage reservoir 46 and 8 contains the medium oils, that is all those white and light colored oils such as kerosene, and suited for illuminating purposes, which may be marketed directly from container 46,

or may be further fractionated as may be desired. The other fraction of oil from container 45 is conducted to a container 47, and comprises all those heavier hydrocarbon oils usually employed for lubricating purposes. The oils from container 47 would ordinarily be further fractionated and refined. If desired the still 45 may be employed to divide the oils from container 43 into a relatively large number of fractions which would be directly conducted to a much larger number of storage reservoirs taking the place of the storage reservoirs 46 and 47.

The method herein disclosed is capable of considerable modification without departing from the spirit of my invention. 1 5

What I claim is:

1. The method of refining petroleum oils, whicln comprises topping the crude oil to separate therefrom fractions liable to produce explosive compounds atnormal atmospheric 10 temperatures, washing the remaining heavier I oils and asphaltum compounds with concentrated sulphuric acid, separating from the acidulated oil an acid sludge, washing the recover therefrom by solution the acidulated oil carried into the acid sludge, returning the petroleum washing medium and recovered acidulated oil to the main body of acidulated oil, neutralizing the acidulated oil, and subsequently fractionating said neutralized oil.

2. The method of refining etroleum oils, which comprises distilling ofl the light and readily volatile oils, washing the remaining heavier oils and asphaltum compounds with concentrated sulphuric acid to separate from the acidulated oil an acid sludge, separating the acidulated oil from the acid slud e, ex tracting the acid sludge with a refined ydrocarbon liquid-solvent, adding said liquid solvent with the substances extracted thereby from the acid Nudge to the main body of pounds with concentrated sulphuric acid, separatin the acid sludge from the main body of acidulated oils, heating the acid sludge moderately, repeatedly washing the heated acid sludge with successive volumes of refined petroleum' to recover therefrom by solution the acidulated oil carried into the acid sludge, adding said repeated Washing materials to the main body of acidulated oil, neutralizing the main body of acidulated oil, separating a soap stock from the neutralized main body of oil and fractionating the main body ofoil after separating the soap stock therefrom.

4:. The method of refining petroleum oils,

which comprises distilling off the light and readily volatile oils at a low temperature,

washing the remainder containing the medium and heavy oils and asphaltum'compounds with concentrated sulphuric acid, separating the acid sludge from the main body of acidulated oils, repeatedly extracting the acid sludge with refined petroleum oil to recover therefrom practically all of the aciduated oil, returning the oil. recovered from the acid sludge to the main body of acidulated oil, repeatedly washing the main body of aciduized oil after separation of soap stock there- 'from. y

In testimony Where f I have affixed my signature.

o rro DIECKMANN. 

